1. Field of the Invention
The present invention relates to a particulate phyllosilicate mixture and use thereof. The particles of phyllosilicate mixture of the present invention possess excellent mechanical strength and abrasion resistance, permit creation of unfavorable phenomena impedimental to reactions and stable operations, such as crumbling or powdering of particles, to be prevented, and in addition have excellent fluidity. Therefore, the particulate phyllosilicate mixture of the present invention is suitable as a catalytic component or as a catalyst.
Phyllosilicates have been extensively used as components for various catalysts or as catalysts per se, as additives for plastics, paints and the like, and, by virtue of excellent feel in use and feel to the hand, as additives for cosmetics and pharmaceuticals. In particular, in many cases, they have been used as a catalytic component or a catalyst for petroleum refining, various chemical reactions, including oxidation/reduction, hydrogenation, dehydrogenation, and alkylation, and polymerization of olefins on a commercial scale.
In general, in a reaction system utilizing a catalyst, for any of a gaseous phase and a liquid phase, the so-called xe2x80x9cheterogeneous catalytic reactionxe2x80x9d mainly takes place, and it is common practice to carry out the reaction in a fixed bed, a moving bed, a spouted bed, a suspended bed or the like. For this reason, for most of the catalysts used, shaping into particles is carried out from the viewpoint of improving the flow of the starting materials and/or the reaction products and the transfer of materials and heat, or alternatively a particulate carrier is prepared followed by supporting of a material, which is to serve as a catalyst, a co-catalyst or the like on the carrier. The particulate phyllosilicate mixture according to the present invention is particularly preferred as the above catalytic component or catalyst.
2. Background Art
In general, phyllosilicates, for both natural and synthetic products, when used in a powder form, are mechanically ground to a powder. Most of them have an irregular particle shape and a small bulk density, contain a large amount of fine powder, and have a wide particle size distribution. Phyllosilicates having such shape and powder properties, when used as a catalytic component or a catalyst, are likely to have poor fluidity, poor, productivity, and render, stable operation difficult due to the presence of the fine powder or the like, so far as the present inventors know.
Conventional methods for improving the shape of the above phyllosilicate include, for example, one which comprises dispersing a water-swellable clay mineral in water and spray-drying the dispersion to prepare granules (Japanese Patent Laid-Open No. 50311/1988), one wherein finely divided mica is heated at the melting temperature and then recrystallized (Japanese Patent Laid-Open No. 263431/1994), and one wherein acid-treated smectite clay is mixed and aggregated to prepare granules (Japanese Patent Laid-Open No. 263421/1994).
Among the above methods, the method using spray drying can simply provide a spherical powder having even particle diameters. This method, however, suffers from the following problems. Specifically, when the concentration of the aqueous dispersion of the water-swellable clay mineral is increased in order to improve the profitability, the viscosity of the slurry is increased to create clogging of nozzles or poor shape. On the other hand, when the concentration of the aqueous dispersion of the water-swellable clay mineral is decreased in order to maintain good viscosity of the slurry, only particles having a small diameter can be prepared, resulting in unsatisfactory productivity.
On the other hand, it has been known that olefins are polymerized with catalysts based on (1) a metallocene compound combined with (2) an aluminoxane as disclosed in Japanese Patent Publication (which will be referred to herein as xe2x80x9cJapanese Kokokuxe2x80x9d) No. 12283/1992, Japanese Patent Laid-Open Publication (which will be referred to herein as xe2x80x9cJapanese Kokaixe2x80x9d) Nos. 19309/1988, 35007/1985 and 167307/1990. The polymerizations with these catalysts have advantages than those obtainable when conventional Ziegler-Natta catalysts are used in that a very higher catalyst activity per the transition metal used and polymers having sharp molecular weight distribution and compositional distribution are obtainable.
However, these catalysts are often soluble in the polymerization system, and this feature may sometimes result in process problems such that the olefin polymers obtained by slurry polymerization or vapor/gas phase polymerization in a particulate form may sometimes have poor granulometric characteristics such as an irregular form of granules, lower bulk densities and higher contents of fines. Furthermore, since these catalysts require higher amount of aluminoxanes when commercially acceptable catalyst activities are required, whereby the activities per the aluminum used are low thus entailing economical problems and necessity of removal of the catalyst residues from the polymers produced.
Some improvements have been proposed to solve these problems. For instance, it is proposed to support one or both of the transition metal compound and the organoaluminum compound on an inorganic oxide such as silica or alumina or on an organic material thereby conduct polymerization of olefins thereover. See Japanese Kokai No. 35007/1985, No. 135408/1985, No. 31404/1986, No. 108610/1986, No. 276805/1986, No. 296008/1986, No. 101303/1989, No. 207303/1989, No. 74412/1991, No. 35 74415/1991, No. 234709/1991 and No. 501869/1981 (PCT). It is also proposed to subject the supported catalysts to preliminary polymerization. See Japanese Kokai No: 234710/1991.
These prior proposals would still entail some problems such that the polymers so produced contain fines or granules of a larger size and have low bulk densities and that the polymerization activities per the solid component of the catalysts are low. Other improvements have also been proposed such that use as catalysts is made of metallocene compounds and aluminoxanes supported on the smectite (Japanese Kokai No. 25214/1993) and use as polymerization catalysts of metallocene compounds, phylloclay minerals which have undergone treatment with metal oxides or precursors to metal oxides followed by calcination and organic aluminoxanes (Japanese Kokai No. 33814/1995).
These improvements proposed may produce satisfactory catalyst activities per the aluminum used, but some problems may still remain unsolved in commercial operation such as crushing of particles or formation of fines depending on the polymerization conditions employed resulting in the lowering in the bulk density of the polymer powder or in the lowering in the fluidity in the vapor phase polymerization. The formation of fines may sometimes cause adhesion of the polymers to or sheeting on the polymerization vessel walls, or cause the clogging within pipings or heat-exchangers used whereby stable operation may sometimes be hindered.
The improvements proposed by the present inventors referred to hereinabove to the granulation of phyllosilicates as disclosed in Japanese Kokai Nos. 301917/1993 and 228621/1995 would not always be fully satisfactory when the phyllosilicates so granulated are used as catalyst supports as referred to hereinabove.
In order to solve the above problems, the present inventors ever granulated the phyllosilicate which had been treated under the specific requirements. As a result, the resultant particles had good powder properties, that is, contained no significant amount of fine powder and coarse particles and had high bulk density (Japanese Patent Laid-Open Nos. 301917/1993 and 228621/1995). However, when a phyllosilicate, which is flaky and has a relatively large particle diameter, such as a phyllosilicate belonging to the mica group is used, even though it could be successfully granulated, the resultant particles often have small bulk density and unsatisfactory strength. Therefore, the particles prepared by the above modified method, when used as a catalyst carrier, is not always satisfactory in the productivity of a contemplated polymer, creation of a fine powder and the like.
The present invention aims to solve the above problems of the prior art and is based on such finding that use of a predetermined mixture of a plurality of types of phyllosilicates having different properties can provide particulate phyllosilicate mixtures having good power properties, that is, high strength and bulk density.
Further, the present invention is based on the discovery that the use as catalyst supports of such phyllosilicates produces in high productivities olefin polymers which are improved in mechanical strengths and wear resistances and which as granules are improved in flowing characteristics and resistant to disintegration to or formation of fines which may hinder stable operation of polymerization.
The present invention, accordingly, presents, in one aspect thereof, a catalyst component for polymerizing olefins which comprises:
Component (A) which is a metallocene compound of a transition metal; and
Component (B) which is a particulate phyllosilicate mixture comprising a phyllosilicate of the smectite group and a phyllosilicate of the mica group, the former comprising 0.1 to 50% by weight of the phyllosilicate mixture.
The present invention, in another aspect thereof, resents a catalyst for polymerizing olefins which comprises the catalyst component for polymerizing olefins comprising he Components (A) and (B) given above and a Component C) which is an organoaluminum compound.
The present invention, in still another aspect, presents a process for polymerizing olefins which comprises contacting an olefin with a catalyst comprising Components (A), (B) and (C) that is optional.
The present invention, in further aspect thereof, presents a particulate phyllosilicate mixture which comprises a phyllosilicate of the smectite group and a phyllosilicate of the mica group, the former comprising 1 to 50% by weight of the phyllosilicate mixture and which meets the requirements of (a) to (c):
(a): the average particle diameter of 20 to 1000 xcexcm, with not more than 20% of the total number of particles being accounted for by particles having a particle diameter of not more than 10 xcexcm;
(b): the crushing strength of the particle of not less than 0.5 MPa as measured with a microcompression tester; and
(c): the bulk density of the particulate mixture of not less than 0.6 g/cm3.
According to the present invention, to begin with, particulate phyllosilicate mixtures can be provided which have excellent powder properties, that is, have an even particle diameter, high strength, and high bulk density and contain no significant amount of fine powder or coarse particles. The particulate phyllosilicate mixture can be used in various applications, for example, as a catalyst component which, particularly when used on a commercial scale, is particularly useful in chemical reactions typified by polymerization of olefins. Utilization of the particulate phyllosilicate mixture having the above excellent properties according to the present invention can provide a catalyst having good fluidity, an olefin polymer, which contains no significant amount of a fine powder and coarse particles and has high bulk density, and a process for producing an olefin polymer which is good in reaction product and transfer of heat.
The present invention depends basically on the unique nature of the particulate phlyllosilicate mixtures.
1. Particulate Phyllosilicate Mixture
 less than General description greater than 
The particulate phyllosilicate mixture of the present invention is a mixture comprising a phyllosilicate belonging to the smectite group and a phyllosilicate belonging to the mica group, the particulate phyllosilicate mixture having a content of the phyllosilicate belonging to the smectite group of 0.1 to 50% by weight. The term xe2x80x9ccomprisingxe2x80x9d means, as is understood as a conventional patent term, not only a mixture consisting of a phyllosilicate belonging to the smectite group and a phyllosilicate belonging to the mica group alone (that is, a mixture consisting of 0.1 to 50% by weight of a phyllosilicate belonging to the smectite group and 50 to 99.9% by weight of a phyllosilicate belonging to the mica group) but also a mixture comprising, in addition to the phyllosilicate belonging to the smectite group and the phyllosilicate belonging to the mica group, a suitable or unavoidable component(s) in a minor amount, for example, in an amount of about 0.1 to 30% by weight based on the phyllosilicate belonging to both the groups.
Preferably, the particulate phyllosilicate mixture according to the present invention simultaneously satisfies, in addition to the above requirement, specific requirements (a) to (c).
The requirement (a) is a requirement for the average particle diameter and the proportion of particles having a diameter of not more than 10 xcexcm in the particulate phyllosilicate mixture according to the present invention. Specifically, the average particle diameter should be 20 to 1000 xcexcm, and the number of particles having a particle diameter of not more than 10 xcexcm is not more than 20% based on the total number of the particles. According to the present invention, the average particle diameter is preferably 20 to 500 xcexcm, particularly preferably 20 to 100 xcexcm, and preferably not more than 15%, particularly preferably not more than 10%, of the total number of the particles is taken accounted for by particles having a diameter of not more than 10 xcexcm. The requirement (a) is preferably such that both the above preferred requirements for the average particle diameter and the amount of the particles having a diameter of not more than 10 xcexcm present are preferably satisfied.
In this case, the measurement of the particles was carried out by means of a particle size distribution measuring apparatus utilizing laser diffractometry (xe2x80x9cLMS-24,xe2x80x9d light source: semiconductor laser (wavelength 670 nm)) manufactured by SEISHIN ENTERPRISE CO., LTD. In the measurement, ethanol was used as a dispersing medium, and the particle diameter distribution and the average particle diameter were determined with the refractive index and the shape factor being respectively 1.33 and 1.0.
The requirement (b) is a requirement for the strength of the phyllosilicate particles of the present invention, specifically such that the crushing strength of the particle is not less than 0.5 MPa as measured with a microcompression tester. The requirement (b) in the present invention is preferably such that the crushing strength is not less than 1.0 MPa. The upper limit is about 40 MPa.
The crushing strength is a value determined by measuring the crushing strength of any 10 particles or more by means of a microcompression tester xe2x80x9cMCTM-500,xe2x80x9d manufactured by Shimadzu Seisakusho Ltd. and calculating the average value, of the measurements, as the crushing strength.
The requirement (c) is for the bulk density of the phyllosilicate paiticles according to the present invention. More specifically, the bulk density should be not less than 0.6 g/cm3, preferably not less than 0.7 g/cm3. The upper limit of the bulk density is about 1.5 g/cm3.
 less than Phyllosilicate Belonging to Smectite Group greater than 
The phyllosilicate belonging to the smectite group used in the particulate phyllosilicate mixture of the present invention is a phyllosilicate belonging to the smectite group among phyllosilicates having a 2:1 layer structure. Representative examples of the phyllosilicate belonging to the smectite group include montmorillonite, beidellite, saponite, nontronite, hectorite, and sauconite. In the present invention, any of natural products and synthetic products may be used. Commercially available products, such as xe2x80x9cKunipiaxe2x80x9d and xe2x80x9cSumectonxe2x80x9d (both products being manufactured by Kunimine Industries Co., Ltd.), xe2x80x9cMontmorllonite K10xe2x80x9d (manufactured by Aldrich and Suedchemie), and xe2x80x9cK-Catalysts seriesxe2x80x9d (manufactured by Suedchemie), may also be used. In the practice of the present invention, they may be used alone or as a mixture of two or more.
If necessary, the phyllosilicate belonging to the smectite group may be ground. When the contemplated particulate phyllosilicate mixture according to the present invention is produced, for example, through a slurry state (described below in detail), the grinding treatment permits the phyllosilicate belonging to the smectite group to be highly dispersed in a slurry dispersing medium. Therefore, in the production of the particulate phyllosilicate mixture by the above method, preferably, the phyllosilicate belonging to the smectite group is ground. In this case, grinding methods are not particularly limited, and grinding utilizing collision of particles against one another by means of a high-speed gas stream or grinding utilizing collision of particles against the wall of a grinding device is one method which can be easily practiced on a commercial scale. Specific devices usable herein include jet mills and single track mills. The size of the particles after the grinding is preferably 0.01 to 50 xcexcm, particularly preferably 0.01 to 30 xcexcm. It is needless to say that the particle diameter and the particle diameter distribution of the particulate phyllosilicate mixture belonging to the smectite group after the grinding, when brought to the particulate phyllosilicate mixture of the present invention, satisfy the above requirement (a).
 less than Phyllosilicate Belonging to Mica Group greater than 
The phyllosilicate, belonging to the mica group, used to prepare the particulate phyllosilicate mixture of the present invention is a phyllosilicate, belonging to the mica group, having a 2:1 type layer structure. Representative examples thereof include commonmica, palagonite, phlogopite, biotite, and lepidolite. In the present invention, any of natural products and synthetic products may be used. xe2x80x9cSynthetic mica Somasifxe2x80x9d (manufactured by CO-OP CHEMICAL CO., LTD.), xe2x80x9cFluorophlogopite,xe2x80x9d xe2x80x9cTetrasilicon Fluoride Mica,xe2x80x9d and xe2x80x9cTeniolitexe2x80x9d (all the above products being manufactured by Topy Industries, Ltd.) and the like, which are commercial products, are representative preferred examples of the phyllosilicate belonging to the mica group. In the present invention, they may be used alone or as a mixture of two or more.
 less than Detailed Description greater than 
The particulate phyllosilicate mixture according to the present invention is a mixture containing the phyllosilicate belonging to the mica group and the phyllosilicate belonging to the smectite group. The content of the phyllosilicate belonging to the smectite group is 0.1 to 50% by weight, preferably 0.5 to 40% by weight, particularly preferably 1 to 30% by weight. When the content of the phyliosilicate belonging to the smectite group is lower than the above range, the crushing strength or the bulk density is unfavorably lowered. On the other hand, when it is higher than the above range, the viscosity of the water slurry in the production of the particulate phyllosilicate mixture by spray granulation is so high that clogging of the nozzle and other unfavorable phenomena occur. When the content is lowered in order to render the viscosity of the slurry suitable, the average particle diameter becomes so small that the requirement (a) may not be satisfied.
In the present invention, both the phyllosilicate belonging to the smectite group and the phyllosilicate belonging to the mica group are preferably ion-exchangeable (or swellable). In this case, the term xe2x80x9cion-exchangeablexe2x80x9d means that the intercalated cation of the phyllosilicate is exchangeable. The term xe2x80x9cswellablexe2x80x9d means that water molecules are incorporated into between layers of the phyllosilicate when it is present together with water, causing the bottom-to-bottom spacing to be increased. The degree of the increase in bottom-to-bottom spacing is at least 1.2 times, preferably at least 1.5 times. The term xe2x80x9cphyllo-xe2x80x9d means the material has a layer structure.
In general, the natural product is in many cases not ion-exchangeable (not swellable), and, in this case, in order to render the natural product ion-exchangeable (or swellable), which is a preferred embodiment, it is preferred to carry out treatment for imparting the ion-exchanging or swelling property. The following chemical treatment is particularly preferred for the above purpose.
Preferably, the above two types of silicates are those chemically treated, In this case, the chemical treatment may be any of surface treatment for removing impurities deposited on the surface and treatment which influences the crystal structure and the chemical composition of the phyllosilicate. Examples of the treatment usable herein include (i) acid treatment, (ii) alkali treatment, (iii) salt treatment, and (iv) organic treatment. These treatments remove impurities present on the surface, exchange intercalated cation, and elute cations of aluminum, silicon, magnesium and the like in the crystal structure. As a result, an ion composite, a molecule composite, an organic composite and the like are formed to vary the surface area, the layer-to-layer spacing, the solid acidity and the like. These treatments may be carried out alone or in combination of two or more. When the ion-exchangeability (or swellability) is imparted or improved in one of or both the silicates as a result of the xe2x80x9cchemical treatmentxe2x80x9d, the xe2x80x9cchemical treatmentxe2x80x9d can be regarded as the xe2x80x9ctreatment for imparting the ion-exchanging (or swelling) property.xe2x80x9d These chemical treatments may be applied to any one of or both the phyllosilicate belonging to the smectite group and the phyllosilicate belonging to the mica group before mixing of both the phyllosilicates or alternatively may be applied to both the phyllosilicates after the mixing.
Acids (i) usable in the chemical treatment include suitable inorganic acids or organic acids, and preferred examples thereof include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and oxalic acid. Alkalis (ii) usable in the chemical treatment include NaOH, KOH, and NH3. Salts (iii) usable in the chemical treatment are preferably a compound comprising a cation, containing at least one atom selected from the group consisting of the Groups 2 to 14 atoms, and at least one anion selected from the group consisting of anions derived from halogen atoms or inorganic or organic acids. More preferred is a salt comprising a cation derived from aluminum, magnesium, titanium, zirconium, hafnium, chromium, zinc, tin, copper, nickel, iron, niobium, or thallium and an anion derived from Cl, SO4, NO3, OH, C2H4, or PO4. Organic materials (iv) usable in the chemical treatment include alcohols (aliphatic alcohols having 1 to 4 carbon atoms, preferably, for example, methanol, ethanol, propanol, ethylene glycol, glycerin, and aromatic alcohols having 6 to 8 carbon atoms, preferably, for example, phenol) and higher hydrocarbons (hydrocarbons having 5 to 10 carbon atoms, preferably 5 to 8 carbon atoms, preferably, for example, hexane and heptane). Other preferred examples thereof include formamide, hydrazine, dimethylsulfoxide, N-methyformamide, and N,N-dimethylanilide. In this case, the Periodic Table of atoms is based on a 18-group system recommended by IUPAC in 1989.
When the particulate phyllosilicate mixture does not simultaneously satisfy the requirements (a) to (c), or in order to bring the particulate phyllosilicate mixture into a more preferred form even though the above requirements are simultaneously satisfied, the properties of the particles can be regulated, for example, by granulation, sieving, classification and the like. The method may be any suitable method. Regarding the granulation, examples of methods usable herein include spray granulation, tumbling granulation, compression granulation, agitation granulation, briquetting, compacting, extrusion granulation, fluidized bed granulation, emulsion granulation, and submerged granulation. Among the above methods, spray granulation, tumbling granulation, and compression granulation are particularly preferred.
When the properties of the particle are regulated, a mixture containing the phyllosilicate belonging to the smectite group and the phyllosilicate belonging to the mica group may be previously brought to a form suitable for the regulation method. For example, when spray granulation is adopted for regulating the properties of the particle, preferably, the above mixture is previously dispersed in a dispersing medium to prepare a slurry.
The dispersing medium used in the spray granulation is preferably water or an organic material (for example, methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene). These dispersing media may be used alone or as a mixture of two or more. Among them, water is particularly preferred. The concentration of the slurry is 5 to 70% by weight, preferably 10 to 50% by weight, more preferably 20 to 40% by weight. The optimal concentration of the slurry may be properly selected by taking the viscosity of the slurry into consideration. Specifically, the concentration of the slurry is not more than 6000 cps, preferably 10 to 5000 cps, particularly 1000 to 3000 cps.
In the present invention, the viscosity of the slurry is a value as measured with a Brookfield viscometer at 30xc2x0C. and 6 rpm. When the viscosity exceeds 6000 cps, the feed of the liquid into the spray nozzle is difficult and, in addition, clogging of the nozzle and other unfavorable phenomena are likely to occur. When the concentration of the slurry is lowered in order to lower the viscosity, there is tendency that only small particles can be produced. Although the diameter of the particles prepared by granulation varies depending upon the spray speed, a slurry concentration of less than 5% makes it difficult to prepare particles having a diameter of not less than 10 xcexcm. In the spray granulation, a conventional spray drying method may be applied such as a disc type or pressure nozzle or two-fluid nozzle type drying method. In any case, the input temperature of the hot air at the time of spraying may be set in a wide temperature range of from about 150 to 300xc2x0 C. Although the exhaust temperature is specified by the spray flow rate through the nozzle and the like, it is preferably about 100xc2x0 C.
Therefore, one representative, simple, and economical process for producing the particulate phyllosilicate mixture of the present invention comprises subjecting a mixed powder composed of the phyllosilicate belonging to the mica group and the phyllosilicate belonging to the smectite group to ion exchange treatment, dispersing the resultant ion exchanged product in a dispersing medium to prepare a slurry, and spray-granulating the slurry. In this case, the content of the phyllosilicate belonging to the smectite group is preferably 10 to 50% by weight, particularly preferably 30 to 50% by weight.
Another representative, simple, economical process comprises dispersing the phyllosilicate belonging to the mica group, which has been subjected to ion exchange treatment, in a dispersing medium to prepare a slurry, adding a slurry of the phyllosilicate belonging to the smectite group, which has not been subjected to ion exchange treatment, mixing the slurries together, and spray-granulating the mixed slurry. In this case, the amount of the phyllosilicate belonging to the smectite group added is 0.1 to 30% by weight, particularly preferably 0.1 to 15% by weight. This can provide a granulated product having high strength and high bulk density.
Typical particulate phyllosilicate mixtures suitable for use as a carrier as Component (B) for the catalysts for polymerizing olefins in the present invention include:
those where the particulate phyllosilicate of the mica group is ion-exchangeable;
those where the particulate phyllosilicate of the mica group has not less than 30% of the exchangeable cations exchanged with a cation of an element of Groups 2 to 14 of Periodic Table or H+; and
those where the particulate phyllosilicate mixtures have not less than 30% all the exchangeable cations contained therein exchanged with a cation of an element of Group 2 to 14 of Periodic Table.
2. Catalyst for Polymerization of Olefin
The particulate phyllosilicate mixture of the present invention is suitably usable particularly as a carrier for a catalytic component for the polymerization of an olefin. Especially preferably, the particulate phyllosilicate mixture may be effectively used in a catalyst, for the polymerization of an olefin, comprising a metallocene transition metal compound, an organoaluminum compound, Land optional other compound(s).
The catalyst for polymerizing olefins in accordance with the present invention comprises Component (A) which is a metallocene compound of a transition metal and Component (B) which is a particulate phyllosilicate mixture comprising a phyllosilicate of the smectite group and a phyllosilicate of the mica group, the former comprising 1 to 50% by weight of the phyllosilicate mixture.
 less than Metallocene Compound of Transition Metal/Component (A) greater than 
The metallocene compounds of transition metals in the catalyst of the present invention may be those used in conventional metallocene catalysts for the polymerization of an olefin. For example, it may be an organometal compound comprising an optionally substituted one or two cyclopentadienyl ligands, that is, one or two cyclopentadienyl ring-containing ligand, with substituent being optionally combined to form a condensed ring, and a group 3, 4, 5, or 6 transition metal of the long form of the Periodic Table, or a cationic complex thereof. The Periodic Table herein means the one based on the 18 Groups recommended by IUPAC in 1989.
Preferred metallocene compounds include compounds represented by the following general formulae [1] and [2]:
(CpR1aH5xe2x88x92a)p(CpR2bH5xe2x88x92b)qMR3rxe2x80x83xe2x80x83[1]
[(CpR1aH5xe2x88x92a)p(CpR2bH5xe2x88x92b)qMR3r Lm]n+[R4]xe2x80x83xe2x80x83[2]
In the formulae [1] and [2], Cp represents a conjugated, five-membered ring ligand and R1 and R2 represent a substituent on Cp. Therefore, CpR1aH5xe2x88x92a and CpR2bH5xe2x88x92b represent derivatives of a cyclopentadienyl (Cp) group.
R1 and R2 each independently represent an optionally substituted hydrocarbon group (when substituted, the substituent being preferably, for example, an alkyl group of 1 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms, or a halogen atom), a silicon-containing group, a phosphorus-containing group, a nitrogen-containing group, and an oxygen-containing group, having 1 to 30 carbon atoms. When a plurality of R1s and R2s are present, all of R1s and R2s do not need respectively to represent the same group and R1 and R2 may be the same or different.
The examples of R1 and of R2 include (i) hydrocarbon groups such as (a) alkyl groups of 1 to 30, preferably 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups, (b) aryl groups of 6 to 30, preferably 6 to 20 carbon atoms such as phenyl, p-tolyl, o-tolyl, and m-tolyl groups, (ii) halo-derivatives of the hydrocarbon group of (i) such as fluoromethyl, fluoroethyl, fluorophenyl, chloromethyl, chloroethyl, chlorophenyl, bromomethyl, bromoethyl, bromophenyl, iodomethyl, iodoethyl, and iodophenyl groups, (iii) silicon-containing hydrocarbon groups of 1 to 30, preferably 1 to 10 carbon atoms such as trimethylsilyl, triethylsilyl, and triphenylsilyl groups, (iv) phosphorus-containing hydrocarbon groups of 1 to 30, preferably 1 to 12 carbon atoms such as dimethylphosphino, diethylphosphino, and diphenylphosphino groups, (v) nitrogen-containing hydrocarbon groups of 1 to 30, preferably 1 to 10 carbon atoms such as dimethylamino, diethylamino, and diisopropylamino groups, (vi) oxygen-containing hydrocarbon groups of 1 to 30, preferably 1 to 20 carbon atoms such as (a) alkoxy groups such as methoxy, ethoxy, and t-butoxy groups, and (b) aryloxy groups such as phenoxy, methylphenoxy, pentamethylphenoxy, p-tolyloxy, m-tolyloxy, and o-tolyloxy groups.
Among these, more preferable R1 and R2, respectively, include alkyl groups of 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl groups, alkyl-substituted silicon-containing groups of preferably 1 to 4 carbon atoms in the alkyl such as trimethylsilyl; alkoxy groups of 1 to 4 carbon atoms such as methoxyl group; and aryloxy groups such as phenoxy group.
The two cyclopentadienyl group may or may not be combined through a bridge. The bridge can be construed as consisting of the R1 and R2 combined with each other at their w-terminus when respectively at least one R1 and R2 are present on the cyclopentadienyl groups.
Specific examples of the bridge include (i) alkylene groups of 1 to 30, preferably 1 to 20 carbon atoms, for example, methylene and ethylene groups, (ii) alkylidene groups of 1 to 20 carbon atoms, for example, ethylidene and propylidene groups, (iii) silicon-containing bridge groups of 1 to 20 carbon atoms, particularly substituted or unsubstituted silylene or oligosilylene groups (with the substituent being preferably a lower alkyl group (having 4 or less carbon atoms)), for example, dimethylsilylene, diethylsilylene, diisopropylsilylene, diphenylsilylene, methylethylsilylene, methylphenylsilylene, methylisopropylsilylene and methyl-t-butylsilylene groups, (iv) germanium-containing bridge groups of 1 to 20 carbon atoms, particularly substituted or unsubstituted germylene or oligogermylene groups (wherein the substituent is preferably a lower alkyl group having about four or less carbon atoms), for example, dimethylgermylene, diethylgermylene, dipropylgermylene, diisopropylgermylene, methylethylgermylene, methylphenylgermylene, methylisopropylgermylene and methyl-t-butylgermylene groups., (v) N-containing groups such as amino groups wherein, in the case of secondary or tertiary amino groups, the substituent is preferably a lower alkyl group having four or less carbon atoms, (vi) P-containing groups, such as a phosphinyl group, and (vii) a direct linkage.
When two or more of R1s (or R2s) are present on an identical Cp, the R1s at their xcfx89-ends (or R2s at their xcfx89-ends) can combine with each other to form a ring.
A specific example thereof is a structure wherein two R1s, in their xcfx89-ends, bonded respectively to two adjacent carbon atoms in Cp combine with each other to own the two carbon atoms in Cp jointly, thereby forming a condensed ring, typically an indenyl or fluorenyl group. The condensed ring derived from R1 may be an unsubstituted one (in the case of the above compound, examples of the unsubstituted condensed ring including tetrahydroindenyl and octahydrofluorenyl groups) or a substituted one (examples of preferred substituents including methyl, ethyl, butyl, and phenyl groups). The condensed ring derived from R1 is an unsubstituted one means that the total number of carbon atoms of the two R1s is equal to the number of carbon atoms necessary for the condensed ring. When the total number of carbon atoms of the two R1s is larger than the number of carbon atoms necessary for the condensed ring, the excess number of carbon atoms serve as a substituent. As with R1, R2 bonded to another Cp in an identical compound can form a condensed ring.
R3 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (examples of preferred substituents including methyl, ethyl, and benzyl groups), hydrogen, a halogen, a silicon-containing substituent, an alkoxy group, an aryloxy group, an amido group, a thioalkoxy group, S(O)s, R5, OR5, NR5t, SiR5, or P(O)uR53 wherein s is 0, 1, 2, or 3, t is 0, 1, 2, or 3, u is 0, 1, 2, or 3 and R5 which may be the same or different represent hydrogen, a halogen, a silicon-containing group, or an optionally halogen-substituted hydrocarbon group having 1 to 20 carbon atoms.
Specific examples of preferred R3 include (i) alkyl groups, particularly methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups, (ii) aryl groups, particularly phenyl groups, p-tolyl, o-tolyl, and m-tolyl groups, (iii) halo-substituted hydrocarbon groups, particularly fluoromethyl, fluoroethyl, fluorophenyl, fluorophenyl, chloromethyl, chloroethyl, chlorophenyl, bromomethyl, bromoethyl, bromophenyl, iodomethyl, iodoethyl, and iodophenyl groups, (iv) halogens, particularly fluorine, chlorine, bromine, and iodine, (v) silicon-containing group, particularly trimethylsilyl, triethylsilyl, and triphenylsilyl groups, (vi) alkoxy, preferably lower alkyloxy groups, particularly methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and t-butoxy groups, (vii) aryloxy groups, particularly phenoxy, methylphenoxy, pentamethylphenoxy, p-tolyloxy, m-tolyloxy, and o-tolyloxy groups, (viii) amide groups, preferably di-lower-alkyl amido groups, particularly dimethylamido, diethylamido, dipropylamido, diisopropylamido, ethyl-t-butylamido, and bis(trimethylsilyl)amido, (ix) thioalkoxy group, preferably lower alkylthio lower alkyloxy groups, particularly a methylthioalkoxy, ethylthioalkoxy, propylthioalkoxy, butylthioalkoxy, t-butylthioalkoxy, and phenylthioalkoxy groups, and (x) hydrogen. Among them, more preferable are hydrogen, methyl, ethyl, propyl, isopropyl, butyl, phenyl groups, halogen, particularly chloride, methoxy, ethoxy, propoxy, isopropoxy, dimethylamido, and methylthioalkoxy groups, hydrogen, methyl and chlorine being most preferable.
In addition to the above typical examples of R1 to R3, R3 can combine with R1, R2, or Cp. Specific examples of preferred ligands include CpH4(CH2)nOxe2x80x94(1xe2x89xa6nxe2x89xa65), CpMe4(CH2)nOxe2x80x94(1xe2x89xa6nxe2x89xa65), CpH4(Me2Si)(txe2x80x94Bu)Nxe2x80x94, and CpMe4(Me2Si)(txe2x80x94Bu)Nxe2x80x94 wherein Cp represents a cyclopentadienyl group, Me represents a methyl group and Bu represents a butyl group). Further, R3s when present in plural can combine with each other to form a bidentate ligand. Specific examples of such R3 include xe2x80x94OCH2Oxe2x80x94, xe2x80x94OCH2CH2Oxe2x80x94 and xe2x80x94O(o-C6H4)Oxe2x80x94. R1 to R3 in the nontypical examples of R1 to R3 are as defined in the case of typical examples so far as there is no contradiction.
M represents a Group 3, 4, 5, or 6 element of the Periodic Table, and specific examples thereof include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, rutetium, actinium, thorium, protactinium, uranium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten. Among them, titanium, zirconium, and hafnium belonging to the Group 4 of the Periodic Table are preferred. Further, they can be used as a mixture of two or more.
L represents an electrically neutral ligand, and m represents an integer of 0 (zero) or more. Specific examples thereof include (i) ethers, especially monoethers, particularly ethers with the hydrocarbon, bonded to ether oxygen, having about 1 to 5 carbon atoms, for example, diethyl ether, tetrahydrofuran, and dioxane, (ii) nitriles, especially those with the hydrocarbon, bonded to a cyano group, having about 1 to 6 carbon atoms, for example, acetonitrile, (iii) amides, especially N,N-di-lower-alkyl lower fatty acid amides, for example, dimethylformamide, (iv) phosphines, especially tri-lower-alkylphosphines and triphenylphosphine, for example, trimethylphosphine, and (v) amines, especially lower-alkylamines, for example, trimethylamine. Particularly preferred are tetrahydrofuran, trimethylphosphine, and trimethylamine.
[R4] represents an anion for neutralizing a cation, and the number of R4s is 1 or not less than 2. Specific examples of [R4] include tetraphenyl borate, tetra(p-tolyl) borate, carbadodecaborate, dicarbaundecaborate, tetrakis(pentafluorophenyl) borate, tetrafluoroborate, hexafluorophosphate. That is, preferred examples of R4 include borates containing a hydrocarbon or halohydrocarbon having about 1 to 30 carbon atoms, or a halogen, and phosphates containing the above groups. Tetraphenyl borate, tetra (p-tolyl) borate, tetrafluoroborate and hexafluorophosphate being preferable.
a and b each independently are an integer of 0 to 5. When the metallocene compound is represented by the formula [1], p, q, and r are zero or a positive, satisfying p+q+r=V wherein V represents the valency of M, and, when the metallocene compound is represented by the formula [2], p, q, and r are zero or a positive, satisfying p+q+r=Vxe2x88x92n wherein V is as defined above. In general, p and q are an integer of 0 to 3, preferably 0 or 1. r is an integer of 0 to 3, preferably 1 or 2. n is an integer satisfying 0xe2x89xa6nxe2x89xa6V.
Specific examples of preferred zirconium compounds in metallocene transition metal compounds represented by the formula [1], among the above metailocene transition metal compounds, include:
(1) bis(methylcyclopentadienyl)zirconium dichloride,
(2) bis(ethylcyclopentadienyl)zirconium dichloride,
(3) bis(methylcyclopentadienyl)zirconium dimethyl,
(4) bis(ethylcyclopentadienyl)zirconium dimethyl,
(5) bis(methylcyclopentadienyl)zirconium dihydride,
(6) bis(ethylcyclopentadienyl)zirconium dihydride,
(7) bis(dimethylcyclopentadienyl) zirconium dichloride,
(8) bis(trimethylcyclopentadienyl)zirconium dichloride,
(9) bis(tetramethylcyclopentadienyl)zirconium dichloride,
(10) bis(ethyltetramethylcyclopentadienyl)zirconium dichloride,
(11) bis(indenyl)zirconium dichloride,
(12) bis(dimethylcyclopentadienyl)zirconium dimethyl,
(13) bis(trimethylcyclopentadienyl)zirconium dimethyl,
(14) bis(tetramethylcyclopentadienyl)zirconium dimethyl,
(15) bis(ethyltetramethylcyclopentadienyl)zirconium dimethyl,
(16) bis(indenyl)zirconium dimethyl,
(17) bis(dimethylcyclopentadienyl)zirconium dihydride,
(18) bis(trimethylcyclopentadienyl)zirconium dihydride,
(19) bis(ethyltetramethylcyclopentadienyl)zirconium dihydride,
(20) bis(trimethylsilylcyclopentadienyl)zirconium dimethyl,
(21) bis(trimethylsilylcyclopentadienyl)zirconium dihydride,
(22) bis(trifluoromethylcyclopentadienyl)zirconium dichloride,
(23) bis(trifluoromethylcyclopentadienyl)zirconium dimethyl,
(24) bis(trifluoromethylcyclopentadienyl)zirconium dihydride,
(25) isopropylidene-bis(indenyl)zirconium dichloride,
(26) isopropylidene-bis(indenyl)zirconium dihydride,
(27) isopropylidene-bis(indenyl)zirconium dihydride,
(28) pentamethylcyclopentadienyl(cyclopentadienyl)-zirconium dichloride,
(29) pentamethylcyclopentadienyl(cyclopentadienyl)-zirconium dimethyl,
(30) pentamethylcyclopentadienyl(cyclopentadienyl)-zirconium dihydride,
(31) ethyltetramethylcyclopentadienyl (cyclopentadienyl)zirconium dihydride,
(32) isopropylidene(cyclopentadienyl)(fluorenyl)-zirconium dichloride,
(33) isopropylidene (cyclopentadienyl)(fluorenyl)-zirconium dimethyl,
(34) dimethylsilyl(cyclopentadienyl)(fluorenyl)-zirconium dimethyl,
(35) isopropylidene(cyclopentadienyl)(fluorenyl)-zirconium dihydride,
(36) bis(cyclopentadienyl)zirconium dichloride,
(37) bis(cyclopentadienyl)zirconium dimethyl,
(38) bis(cyclopentadienyl)zirconium diethyl,
(39) bis(cyclopentadienyl)zirconium dipropyl,
(40) bis(cyclopentadienyl)zirconium diphenyl,
(41) methylcyclopentadienyl(cyclopentadienyl)-zirconium dichloride,
(42) ethylcyclopentadienyl(cyclopentadienyl)zirconium dichloride,
(43) methylcyclopentadienyl(cyclopentadienyl)-zirconium dimethyl,
(44) ethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl,
(45) methylcyclopentadienyl(cyclopentadienyl)-zirconium dihydride,
(46) ethylcyclopentadienyl (cyclopentadiethyl)zirconium dihydride,
(47) dimethylcyclopentadienyl(cyclopentadienyl)-zirconium dichloride,
(48) trimethylcyclopentadienyl(cyclopentadienyl)-zirconium dichloride,
(49) tetramethylcyclopentadienyl(cyclopentadienyl)-zirconium dichloride,
(50) bis(pentamethylcyclopentadienyl)zirconium dichloride,
(51) tetramethylcyclopentadienyl(cyclopentadienyl)-zirconium dichloride,
(52) indenyl(cyclopentadienyl)zirconium dichloride,
(53) dimethylcyclopentadienyl(cyclopentadienyl)-zirconium dimethyl,
(54) trimethylcyclopentadienyl(cyclopentadienyl)-zirconium dimethyl,
(55) tetramethylcyclopentadienyl(cyclopentadienyl)-zirconium dimethyl,
(56) bis(pentamethylcyclopentadienyl)zirconium dimethyl,
(57) ethyltetramethylcyclopentadienyl (cyclopentadienyl)zirconium dimethyl,
(58) indenyl(cyclopentadienyl)zirconium dimethyl,
(59) dimethylcyclopentadienyl(cyclopentadienyl)-zirconium dihydride,
(60) trimethylcyclopentadienyl(cyclopentadienyl)-zirconium dihydride,
(61) bis(pentamethylcyclopentadienyl)zirconium dihydride,
(62) indenyl(cyclopentadienyl)zirconium dihydride,
(63) trimethylsilylcyclopentadienyl(cyclopentadienyl)-zirconium dimethyl,
(64) trimethylsilylcyclopentadienyl(cyclopentadienyl)-zirconium dihydride,
(65) trifluoromethylcyclopentadienyl-(cyclopentadienyl)-zirconium dichloride,
(66) trifluoromethylcyclopentadienyl-(cyclopentadienyl) zirconium dimethyl,
(67) trifluoromethylcyclopentadienyl-(cyclopentadienyl) zirconium dihydride,
(68) bis(cyclopentadienyl)(trimethylsilyl)(methyl)-zirconium,
(69) bis(cyclopentadienyl) (triphenylsilyl) (methyl)-zirconium,
(70) bis(cyclopentadienyl)[tris(trimethylsilyl)silyl]-(methyl)zirconium,
(71) bis(cyclopentadienyl)[bis(methylsilyl)silyl](methyl)zirconium,
(72) bis(cyclopentadienyl)(trimethylsilyl)(trimethylsilylmethyl)zirconium,
(73) bis(cyclopentadienyl)(trimethylsilyl)(benzyl)zirconium,
(74) methylene-bis(cyclopentadienyl)zirconium dichloride,
(75) ethylene-bis(cyclopentadienyl)zirconium dichloride,
(76) isopropylidene-bis(cyclopentadienyl)zirconium dichloride,
(77) dimethylsilyl-bis(cyclopentadienyl)zirconium dichloride,
(78) methylene-bis(cyclopentadienyl)zirconium dimethyl,
(79) ethylene-bis(cyclopentadienyl)zirconium dimethyl,
(80) isopropylidene-bis(cyclopentadienyl)zirconium dimethyl,
(81) dimethylsilyl-bis(cyclopentadienyl)zirconium dimethyl,
(82) methylene-bis(cyclopentadienyl)zirconium dihydride,
(83) ethylene-bis(cyclopentadienyl)zirconium dihydride,
(84) isopropylidene-bis(cyclopentadienyl)zirconium dihydride,
(85) dimethylsilyl-bis(cyclopentadienyl)zirconium dihydride,
(86) bis(cyclopentadienyl)zirconium bis(methanesulfonato),
(87) bis(cyclopentadienyl)zirconium bis(p-toluenesulfonato),
(88) bis(cyclopentadienyl)zirconium bis(trifluoromethanesulfonato)
(89) bis(cyclopentadienyl)zirconium trifluoromethanesulfonato chloride,
(90) bis(cyclopentadienyl)zirconium bis(benzenesulfonato),
(91) bis(cyclopentadienyl)zirconium bis(pentafluorobenzenesulfonato),
(92) bis(cyclopentadienyl)zirconium benzene sulfonato chloride,
(93) bis(cyclopentadienyl)zirconium(ethoxy)-trifluoromethanesulfonato,
(94) bis(tetramethylcyclopentadienyl)zirconium bis(trifluoromethanesulfonato),
(95) bis(indenyl)zirconium bis(trifluorome thanesulfonato),
(96) ethylene-bis(indenyl)zirconium bis(trifluoromethanesulfonato),
(97) isopropylidene-bis(indenyl)zirconium bis(trifluoromethanesulfonato),
(98) (tert-butylamido)dimethyl-(tetramethylcyclopentadienyl)silanedibenzylzirconium(tert-butylamido)dimethyl(2,3,4,5-tetramethylcyclopentadienyl)silanedibenzylzirconium,
(99) indenylzirconium tris(dimethylamido),
(100) indenylzirconium tris(diethylamido),
(101) indenylzirconium tris(di-n-propylamido),
(102) cyclopentadienylzirconium tris(dimethylamido),
(103) methylcyclopentadienylzirconium tris(dimethylamido),
(104) (tert-butylamido)(tetramethylcyclopentadienyl)-1,2-ethanediylzirconium dichloride,
(105) (methylamido)-(tetramethylcyclopentadienyl)-1,2-ethanediylzirconium dichloride,
(106) (ethylamido)(tetramethylcyclopentadienyl)-methylenezirconium chloride,
(107) (tert-butylamido)dimethyl-(tetramethylcyclopentadienyl)silanezirconium dichloride,
(108) (benzylamido)dimethyl-(tetramethylcyclopentadienyl)silanezirconium dichloride,
(109) (phenylphosphido)dimethyl-(tetramethylcyclopentadienyl)silanezirconium dichloride and dibenzyl,
(110) (benzylamido)dimethyl-(tetramethylcyclopentadienyl)silanezirconium dichloride,
(111) (2-methoxyphenylamido)dimethyl-(tetramethylcyclopentadienyl)silanezirconium dichloride,
(112) (4-fluorophenylamido)dimethyl-(tetramethylcyclopentadienyl)silanezirconium dichloride,
(113) ((2,6-di(1-methylethyl)phenyl)amido)dimethyl-(tetramethylcyclopentadienyl)amidozirconium dichloride,
(114) bis(1,3-dimethylcyclopentadienyl)zirconium dichloride,
(115) bis(1-ethyl-3-methylcyclopentadienyl)zirconium dichloride,
(116) bis(1-n-propyl-3-methylcyclopentadienyl)-zirconium dichloride,
(117) bis(1-1-propyl-3-methylcyclopentadienyl)zirconium dichloride,
(118) (bis-1-n-butyl-3-methylcyclopentadienyl)-zirconium dichloride,
(119) bis(1-1-butyl-3-methylcyclopentadienyl)zirconium dichloride,
(120) bis(1-cyclohexyl-3-methylcyclopentadienyl)zirconium dichloride,
(121) bis(1,3-dimethylcyclopentadienyl)zirconium dimethyl,
(122) bis(1-ethyl-3- methylcyclopentadienyl)zirconium dimethyl,
(123) bis(1-n-propyl-3-methylcyclopentadienyl)-zirconium dimethyl,
(124) bis(1-n-butyl-3-methylcyclopentadienyl)zirconium dimethyl,
(125) bis(1,3-dimethylcyclopentadienyl)zirconium bis(diethylamido),
(126) bis(1-ethyl-3-methylcyclopentadienyl)zirconium bis(diethylamido), and
(127) bis(1-n-butyl-3-methylcyclopentadienyl)zirconium bis(diethylamido).
Specific examples of preferred zirconium compounds in metallocene compounds represented by the formula [2] include:
(1) bis(methylcyclopentadienyl)zirconium (chloride) (tetraphenyl borate)tetrahydrofuran complex,
(2) bis(ethylcyclopentadienyl)zirconium (chloride) (tetraphenyl borate)tetrahydrofuran complex,
(3) bis(methylcyclopentadienyl)zirconium (methyl) (tetraphenyl borate)tetrahydrofuran complex,
(4) bis(ethylcyclopentadienyl)zirconium (methyl) (tetraphenyl borate)tetrahydrofuran complex,
(5) bis(methylcyclopentadienyl)zirconium (hydride) (tetraphenyl borate)tetrahydrofuran complex,
(6) bis(ethylcyclopentadienyl)zirconium (hydride) (tetraphenyl borate)tetrahydrofuran complex,
(7) bis(dimethylcyclopentadienyl)zirconium (chloride) (tetraphenyl borate)tetrahydrofuran complex,
(8) bis(trimethylcyclopentadienyl)zirconium (chloride) (tetraphenylborate)tetrahydrofuran complex,
(9) bis(tetramethylcyclopentadienyl)zirconium (chloride) (tetraphenylborate)tetrahydrofuran complex,
(10) bis(ethyltetramethylcyclopentadienyl)zirconium (chloride) (tetraphenylborate)tetrahydrofuran complex,
(11) bis(indenyl)zirconium (chloride) (tetraphenyl borate)tetrahydrofuran complex,
(12) bis(dimethylcyclopentadienyl)zirconium (methyl) (tetraphenyl borate)tetrahydrofuran complex,
(13) bis(trimethylcyclopentadienyl)zirconium (methyl) (tetraphenylborate)tetrahydrofuran complex,
(14) bis(tetramethylcyclopentadienyl)zirconium (methyl) (tetraphenylborate)tetrahydrofuran complex,
(15) bis(ethyltetramethylcyclopentadienyl)zirconium (methyl) (tetraphenylborate)tetrahydrofuran complex,
(16) bis(indenyl)zirconium (methyl) (tetraphenylborate)tetrahydrofuran complex,
(17) bis(dimethylcyclopentadienyl)zirconium (hydride) (tetraphenylborate)tetrahydrofuran complex,
(18) bis(trimethylcyclopentadienyl)zirconium (hydride) (tetraphenyl borate)tetrahydrofuran complex,
(19) bis(ethyltetramethylcyclopentadienyl)zirconium (hydride) (tetraphenylborate)tetrahydrofuran complex,
(20) bis(trimethylsilylcyclopentadienyl)zirconium (methyl) (tetraphenylborate)tetrahydrofuran complex,
(21) bis(trimethylsilylcyclopentadienyl)zirconium (hydride)(tetraphenylborate)tetrahydrofuran complex,
(22) bis(trifluoromethylcyclopentadienyl)zirconium (methyl) (tetraphenylborate)tetrahydrofuran complex,
(23) bis(trifluoromethylcyclopentadienyl)zirconium (hydride) (tetraphenylborate)tetrahydrofuran complex,
(24) isopropylidene-bis(indenyl)zirconium (chloride) (tetraphenyl borate)tetrahydrofuran complex,
(25) isopropylidene-bis(indenyl)zirconium (methyl) (tetraphenyl borate)tetrahydrofuran complex,
(26) isopropylidene-bis(indenyl)zirconium (hydride) (tetraphenyl borate)tetrahydrofuran complex,
(27) pentamethylcyclopentadienyl(cyclopentadienyl)zirconium (chloride) (tetraphenyl borate)tetrahydrofuran complex,
(28) ethyltetramethylcyclopentadienyl(cyclopentadienyl)zirconium (chloride) (tetraphenylborate)tetrahydrofuran complex,
(29) pentamethylcyclopentadienyl (cyclopentadienyl)zirconium (methyl) (tetraphenylborate)-tetrahydrofuran complex,
(30) ethyltetramethylcyclopentadienyl(cyclopentadienyl)zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex,
(31) pentamethylcyclopentadienyl)zirconium (hydride) (tetraphenylborate)tetrahydrofuran complex,
(32) ethyltetramethylcyclopentadienyl)zirconium (hydride) (tetraphenylborate)tetrahydrofuran complex,
(33) isopropylidene(cyclopentadienyl)(fluorenyl)zirconium (chloride) (tetraphenyl borate)tetrahydrofuran complex,
(34) isopropylidene (cyclopentadienyl)(fluorenyl)zirconium (methyl) (tetraphenylborate)tetrahydrofuran complex,
(35) isopropylidene (cyclopentadienyl)(fluorenyl)zirconium (hydride) (tetraphenylborate)tetrahydrofuran complex,
(36) bis(cyclopentadienyl)zirconium (chloride) (tetraphenylborate)tetrahydrofuran complex,
(37) bis(cyclopentadienyl)(methyl)zirconium (tetraphenyl borate)tetrahydrofuran complex,
(38) bis(cyclopentadienyl)(ethyl)zirconium (tetraphenylborate)tetrahydrofuran complex,
(39) bis(cyclopentadienyl)(propyl)zirconium (tetraphenylborate)tetrahydrofuran complex,
(40) bis(cyclopentadienyl)(phenyl)zirconium (tetraphenylborate)tetrahydrofuran complex,
(41) methylcyclopentadienyl(cyclopentadienyl)zirconium (chloride) (tetraphenyl borate)tetrahydrofuran complex,
(42) ethylcyclopentadienyl(cyclopentadienyl)zirconium (chloride) (tetraphenylborate)tetrahydrofuran complex,
(43) bis(ethylcyclopentadienyl)zirconium (chloride) (tetraphenylborate)tetrahydrofuran complex,
(44) methylcyclopentadienyl (cyclopentadienyl)zirconium (methyl) (tetraphenylborate)-tetrahydrofuran complex,
(45) ethylcyclopentadienyl (cyclopentadienyl)zirconium (methyl) (tetraphenylborate)-tetrahydrofuran complex,
(46) methylcyclopentadienyl (cyclopentadienyl)zirconium (hydride) (tetraphenylborate)-tetrahydrofuran complex,
(47) ethylcyclopentadienyl (cyclopentadienyl)zirconium (hydride) (tetraphenylborate)-tetrahydrofuran complex,
(48) dimethylcyclopentadienyl(cyclopentadienl)zirconium (chloride) (tetraphenyl borate)tetrahydrofuran complex,
(49) trimethylcyclopentadienyl (cyclopentadienyl)zirconium (chloride) (tetraphenylborate)-tetrahydrofuran complex,
(50) tetramethylcyclopentadienyl (cyclopentadienyl)zirconium (chloride) (tetraphenylborate)-tetrahydrofuran complex,
(51) bis(pentamethylcyclopentadienyl)zirconium (chloride) (tetraphenylborate)tetrahydrofuran complex,
(52) indenyl(cyclopentadienyl)zirconium (chloride) (tetraphenyl borate)tetrahydrofuran complex,
(53) dimethylcyclopentadienyl (cyclopentadienyl)zirconium (methyl) (tetraphenylborate)-tetrahydrofuran complex,
(54) trimethylcyclopentadienyl(cyclopentadienyl)zirconium (methyl) (tetraphenyl borate)tetrahydrofuran complex,
(55) tetrame thylcyclopentadienyl(cyclopentadienyl)zirconium (methyl) (tetraphenylborate)-tetrahydrofuran complex,
(56) bis(pentamethylcyclopentadienyl)zirconium (methyl) (tetraphenylborate)tetrahydrofuran complex,
(57) cyclopentadienyl(indenyl)zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex,
(58) dimethylcyclopentadienyl (cyclopentadienyl)zirconium (hydride) (tetraphenylborate)-tetrahydrofuran complex,
(59) trimethylcyclopentadienyl (cyclopentadienyl)zirconium (hydride) (tetraphenylborate)-tetrahydrofuran complex,
(60) bis(pentamethylcyclopentadienyl)zirconium (hydride) (tetraphenylborate)-tetrahydrofuran complex,
(61) indenyl(cyclopentadienyl)zirconium (hydride) (tetraphenylborate)tetrahydrofuran complex,
(62) trimethylsilylcyclopentadienyl(cyclopentadienyl)zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex,
(63) trimethylsilylcyclopentadienyl(cyclopentadienyl)zirconium (hydride) (tetraphenylborate)tetrahydrofuran complex,
(64) trifluoromethylcyclopentadienyl(cyclopentadienyl)zirconium (hydride) (tetraphenylborate)tetrahydrofuran complex,
(65) bis(cyclopentadienyl)(trimethylsilyl)zirconium (tetraphenyl borate)tetrahydrofuran complex,
(66) bis(cyclopentadienyl)(triphenylsilyl)zirconium (tetraphenylborate)tetrahydrofuran complex,
(67) bis(cyclopentadienyl)[tris(trimethylsilyl)silyl]zirconium (tetraphenylborate)tetrahydrofuran complex,
(68) bis(cyclopentadienyl)(trimethylsilylmethyl)zirconium (tetraphenyl borate)tetrahydrofuran complex,
(69) bis(cyclopentadienyl)(benzyl)zirconium (tetraphenylborate) tetrahydrofuran complex,
(70) methylene-bis(cyclopentadienyl)zirconium (chloride) (tetraphenylborate)tetrahydrofuran complex,
(71) ethylene-bis(cyclopentadienyl)zirconium (chloride) (tetraphenyl borate)tetrahydrofuran complex,
(72) isopropylidene-bis(cyclopentadienyl)zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex,
(73) dimethylsilyl-bis(cyclopentadienyl)zirconium (chloride) (tetraphenyl borate)tetrahydrofuran complex,
(74) methylene-bis(cyclopentadienyl)zirconium (methyl) (tetraphenylborate)tetrahydrofuran complex,
(75) ethylene-bis(cyclopentadienyl)zirconium (methyl) (tetraphenyl borate)tetrahydrofuran complex,
(76) isopropylidene-bis(cyclopentadienyl)zirconium (methyl) (tetraphenylborate)tetrahydrofuran complex,
(77) dimethylsilyl-bis(cyclopentadienyl)zirconium (methyl)(tetraphenyl borate)tetrahydrofuran complex,
(78) methylene-bis(cyclopentadienyl)zirconium (hydride) (tetraphenylborate)tetrahydrofuran complex, (79) ethylene-bis (cyclopentadienyl)zirconium (hydride) (tetraphenyl borate)tetrahydrofuran complex,
(80) isopropylidene-bis(cyclopentadienyl)zirconium (hydride) (tetraphenylborate)tetrahydrofuran complex,
(81) dimethylsilyl-bis(cyclopentadienyl)zirconium (hydride) (tetraphenylborate)tetrahydrofuran complex,
(82) bis(cyclopentadienyl)zirconium (methanesulfonato) (tetraphenyl borate)tetrahydrofuran complex,
(83) bis(cyclopentadienyl)zirconium (p-toluenesulfonato) (tetraphenylborate)tetrahydrofuran complex,
(84) bis(cyclopentadienyl)zirconium (trifluoromethanesulfonato) (tetraphenylborate)tetrahydrofuran complex,
(85) bis(cyclopentadienyl)zirconium (benzenesulfonato) (tetraphenylborate)tetrahydrofuran complex,
(86) bis(cyclopentadienyl)zirconium (pentafluorobenzenesulfonato) (tetraphenylborate)-tetrahydrofuran complex,
(87) bis(tetramethylcyclopentadienyl)zirconium (trifluoromethanesulfonato) (tetraphenylborate)-tetrahydrofuran complex,
(88) bis(indenyl)zirconium (trifluoromethanesulfonato) (tetraphenylborate)tetrahydrofuran complex,
(89) ethylenebis(indenyl)zirconium (trifluoromethanesulfonato) (tetraphenylborate)-tetrahydrofuran complex, and
(90) isopropylidene-bis(indenyl)zirconium (trifluoromethanesulfonato) (tetraphenylborate)-tetrahydrofuran complex.
Examples of the Group 3, 4, 5, and 6 metal compounds, for example, titanium compounds, hafnium compounds and the like include similar compounds as described above. It is needless to say that a mixture of compounds belonging the same group and/or a mixture of compounds belonging to different groups may also be used.
 less than Phyllosilicate/Component (B) greater than 
The combination of the metallocene compounds/Component (A) referred to hereinabove with the particulate phyllosilicate mixture referred to hereinbefore will make a catalyst for polymerizing olefins.
 less than Organoaluminum Compound/Component (C) greater than 
In general, the above metallocene compounds of transition metal and a combination thereof with the particulate phyllosilicate mixture of the present invention per se has catalytic activity for the polymerization of an olefin. If necessary, however, an organoaluminum compound may be further used in combination. This can provide a better catalyst for the polymerization of an olefin.
In view of this, the metallocene compounds of transition metals or combinations of the metallocene compounds with particulate phyllosilicate mixtures are herein referred interchangeably to xe2x80x9ccatalystsxe2x80x9d and xe2x80x9ccatalyst componentsxe2x80x9d, the latter being the case where organoaluminum compounds are used as co-catalysts.
Accordingly, the present invention also relates to a catalyst for the polymerization of an olefin, comprising a combination of the above metallocene transition metal compound and the organoaluminum compound with the particulate phyllosilicate mixture. The expression comprising a combination of used herein connotes a combination of the above three components and an optional other components(s).
It is believed that the organoaluminum compound used in the polymerization or in the prepolymerization described hereinbelow in more detail in the present invention inhibits a lowering in catalytic activity caused by water and the like present in the polymerization system and at the same time contributes to an improvement in catalytic activity. Therefore, addition of the organoaluminum compound is one of preferred embodiments.
Organoaluminum compounds usable in the present invention include, for example, those represented by the following formula:
A1R6jX3xe2x88x92j
wherein R6 represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms: X represents hydrogen, a halogen, or an alkoxy group; and j is a number represented by 0 less than jxe2x89xa63. Preferred are trialkylaluminums, for example, trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum and tri-n-hexylaluminum; alkylaluminum hydride, for example, diethylaluminum hydride, and diisobutylaluminum hydride; halogen- or alkoxy-containing alkylaluminums, for example, diethylaluminum monochloride and diisobutylaluminum monochloride, and diethylaluminum methoxide diisobutylaluminum methoxide; and alkylaluminum amides, for example, diethylaluminum (diethylamide), and diisobutylaluminum (diethylamide). In addition to the above organoaluminum compounds, aluminoxanes, such as methylaluminoxane, can be used. Among them, trialkylaluminums such as triethylaluminum, trilsobutylaluminum, tri-n-butylaluminum, and tri-n-hexylaluminum are particularly preferred.
Catalytic components, such as the particulate phyllosilicate mixture, Component (B), the transition metal compound such as metallocene, Component (A), and the optional organoaluminum compound, Component (C), may be brought into contact with one another by any method without particular limitation. In the contact of the catalytic components, a catalytic component other than described above, for example, a solid of a polymer, such as polyethylene or polypropylene, or an inorganic oxide, such as silica or alumina, can be allowed to coexist or brought into contact with the other catalytic components.
The contact of the Components (A), (B) and (C) may be carried out in the following typical sequences.
{circle around (1)} Component (A) is contacted with Component (B);
{circle around (2)} Component (A) is contacted with Component (B), followed by the contact further with Component (C);
{circle around (3)} Component (A) is contacted with Component (C), followed by the contact further with Component (B);
{circle around (4)} Component (B) is contacted with Component (C), followed by the contact further with Component (A); and
{circle around (5)} Components (A), (B) and (C) are contacted each other simultaneously.
The contact may be carried out in an inert gas, such as nitrogen gas, or an inert hydrocarbon solvent, such as pentane, hexane, heptane, toluene, or xylene. The contact temperature is preferably between xe2x88x9220xc2x0 C. and the boiling point of the solvent, particularly preferably between room temperature and the boiling point of the solvent.
Regarding the amount of the catalytic components used, the amount of the metallocene compound component (A) is 0.0001 to 10 mmol, preferably 0.001 to 5 mmol, per g of the catalyst carrier, viz. particulate phyllosilicate (B). When the organoaluminum component (C) as an optional component is used, the amount of the organoaluminum compound component (C) is not more than 10,000 mmol, preferably 0.0001 to 10,000 mmol, more preferably 0.1 to 100 mmol, per g of the catalyst carrier (B). When the amount of the catalytic components incorporated is expressed in terms of the transition metal in the metallocene compound to the atomic ratio of aluminum in the organoaluminum, the ratio is 1: not more than 1,000,000, preferably 1:0.1 to 10,000.
The catalyst thus obtained may be used either as such without washing or after washing.
 less than Prepolymerization greater than 
The above catalyst for the polymerization of an olefin according to the present invention can be used, with Component (C) comprised or not comprised, for the polymerization of an olefin, as a catalyst after prepolymerization treatment wherein a minor amount of an olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, is thereby polymerized. Olefins usable in the prepolymerization include, for example, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and xcex1-methylstyrene, xe2x80x9colefinxe2x80x9d thus herein including vinyl aromatics.
In the prepolymerization, if necessary, an organoaluminum component compound (preferably one as described above) may be used in combination with the catalyst. In this case, the amount of the organoaluminum component used is selected so that the atomic ratio of the transition metal in the metallocene compound to the aluminum in the organoaluminum compound is 10 to 10,000.
Preferably, the prepolymerization is carried out in an inert solvent which is preferably inert hydrocarbon solvent such as those referred to hereinabove in respect of the contact of Components (A) to (C), under mild conditions such as temperatures of xe2x88x9220xc2x0 C. to 150xc2x0 C. Further, preferably, the prepolymerization is carried out so that a polymer in an amount of 0.01 to 1,000 g, preferably 0.05 to 300 g, more preferably 0.1 to 100 g, per g of the solid catalyst is produced.
When the prepolymerization is conducted with ethylene as the olefin to be prepolymerized, the polyethylene formed preferably has a weight average molecular weight of no smaller than 30,000, more preferably no smaller than 50,000. Excessively small molecular weight of the polyethylene prepolymerized would sometimes show poor improvement in particulate characteristics or in prevention of crushing of particles.
The catalysts which have undergone the prepolymerization can be used in the form of slurry as the process product of the prepolymerization, or after being washed, or after being dried into powder preferably at a temperature, e.g. of 0xc2x0 C. to 100xc2x0 C. under a reduced pressure or in a dry inert gas flow.
The prepolymerization can be carried out so that solid materials, preferably particulate solid materials, such as polymers such as polypropylenes or inorganic oxides such as silica or alumina are admixed at the time of the prepolymerization or after the prepolymerization product having been dried.
 less than Use of Catalyst for Polymerization of Olefin/polymerization of Olefin greater than 
The catalyst, for the polymerization of an olefin according to the present invention, comprising a combination of a metallocene transition metal compound (A), a particulate phyllosilicate mixture (B), and optionally an organoaluminum compound (C), or the catalyst, for the polymerization of an olefin according to the present invention, obtained by subjecting the above catalyst with or without Component (C) to optional other suitable treatment(s)such as, for example, prepolymerization treatment xe2x80x9cand/or washing, can be contacted with an xcex1-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and optionally other monomer(s) copolymerizable with the xcex1-olefin to conduct polymerization (including homopolymerization or copolymerization (either random or block copolymerization)) of the monomer(s).
Specific examples of particularly preferred olefins usable in the polymerization include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, vinylcycloalkane, ethylidene-norbornene derivatives, styrene, and derivatives of the above olefins.
The polymerization may be carried out in the presence or absence of a solvent, for example, an inert hydrocarbon, such as butane, pentane, hexane, heptane, toluene, or cyclohexane, or a liquefied xcex1-olefin. The temperature is xe2x88x9250xc2x0 C. to 250xc2x0 C., preferably 0 to 200xc2x0 C. Although the pressure is not particularly limited, it is preferably atmospheric pressure to 2000 kgf/cm2.
Polymerization can be conducted in any mode of polymerization such as vapor/gas phase polymerization, slurry polymerization, solution polymerization or high pressure polymerization.
The vapor/gas phase polymerization may be carried out at a temperature of 30xc2x0 C. to 150xc2x0 C., preferably 50xc2x0 C. to 120xc2x0 C., under a pressure of 1 to 50 kg/cm2.
The slurry polymerization may be carried out in the presence of a solvent or a liquid monomer at a temperature of xe2x88x9220xc2x0 C. to 150xc2x0 C., preferably 0xc2x0 C. to 120xc2x0 C., under a pressure of 1 to 50 kg/cm2G, preferably 3 to 30 kg/cm2G.
Hydrogen may or may not be used as a molecular weight modifier in the polymerization system. Further, the polymerization can be carried out in a step-wise manner wherein polymerization temperatures, concentration of the molecular weight modifier, and other process conditions are different from step to step.
The use of the catalysts in accordance with the present invention are conducive to production of particulate polymers of a higher bulk density and of improved shape of particles, and, accordingly, the catalysts in accordance with the present invention are used advantageously in the vapor/gas phase polymerization and the slurry polymerization.
The following examples further illustrate the present invention but are not intended to limit it so far as they do not depart from the subject matter of the invention.
In the following examples and comparative example, the melt flow index (hereinafter referred to as xe2x80x9cMFRxe2x80x9d) was measured under conditions of a temperature of 190xc2x0 C. and a load of 2.16 kg according to the procedure set forth in JIS-6758.
Examples and Comparatives Examples of members suffixed with xe2x80x9caxe2x80x9d are those for the first embodiment of the present invention where it is directed to the particulate phyllosilicates of Component (B) with the requirements (a) to (c) are essential corresponding to Japanese Patent Application No. 109173/1997.